CN102558728A - Reinforced acrylic resin compound material - Google Patents
Reinforced acrylic resin compound material Download PDFInfo
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- CN102558728A CN102558728A CN2012100103583A CN201210010358A CN102558728A CN 102558728 A CN102558728 A CN 102558728A CN 2012100103583 A CN2012100103583 A CN 2012100103583A CN 201210010358 A CN201210010358 A CN 201210010358A CN 102558728 A CN102558728 A CN 102558728A
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Abstract
The invention discloses a reinforced acrylic resin compound material and a preparing process thereof. The compound material contains components of: 50-80 parts of acrylic resin, 10-45 parts of long glass fiber, 0.01-4 parts of accelerating agents, 0.5-8 parts of curing agents and 0-10 parts of auxiliaries. The preparing process includes: stirring and completely dissolving the acrylic resin and the accelerating agents for standby use, mixing the mixture and the curing agents uniformly and feeding materials continuously, adding the long glass fiber, covering a layer of upper film, entering a forming warming regulate and control area and cutting a finished product. The reinforced acrylic resin compound material adopts the acrylic resin and the long glass fiber as main raw materials, adopts the accelerating agents and the curing agents as auxiliary materials and is assisted by the auxiliaries. The formula reasonably improves mechanical performance of the product, various reasonably added stabilizing agents protect performance of the compound material from being damaged for a long period, product price is reduced, and application of the compound material is wider. The reinforced acrylic resin compound material and the preparing process thereof adopt a reasonable processing mode and a reasonable flow path so that a whole production line can operate smoothly.
Description
Technical field
The present invention relates to a kind of matrix material and preparation method thereof, relate in particular to a kind of vinyl resin matrix material and preparation method thereof.
Background technology
The vinylformic acid matrix material has very long history; Have the transparency height, can reuse, advantage such as stability to aging excellence utilized by various countries greatly; But its price is higher, essential more crisp, easy to crack, the shortcoming such as linear expansivity is big of material, is difficult to realize more general application.Fiber-reinforced thermoplastic is one of material with fastest developing speed in the current composite markets, and the general resin that adopts is Vestolen PP 7052, Vilaterm etc., and mechanical serialization production technology and immature.The fiber reinforcement thermosetting material also is one of material with fastest developing speed in the current composite markets in addition; Its each item mechanical property is all very excellent; A plurality of fields such as space flight, building, freight container, anti-corrosion storage tank have been widely used at present; But it can not be reprocessed, reuse, and the volume of smoke of burning generation, and performances such as the anti-yellow of uvioresistant have big gap than polymethylmethacrylate.
Summary of the invention
Technical problem to be solved by this invention provides a kind of long glass fibres and strengthens vinyl resin matrix material and preparation technology thereof; Make the vinyl resin matrix material have excellent mechanical property and more excellent over-all properties, and obtain more rationally, composite material preparation process smoothly.
The present invention is that to solve the problems of the technologies described above the technical scheme of employing following:
A kind of enhancing vinyl resin matrix material, the weight part of its component is: by vinyl resin 50-80 part, long glass fibres 10-45 part, promotor 0.01-4 part, solidifying agent 0.5-8 part, auxiliary agent 0-10 part;
Wherein auxiliary agent comprises one or more in inhibitor, UV light absorber, the photostabilizer;
Described long glass fibres is an alkali free glass fibre.
Described vinyl resin is one or more a mixture of polymethylmethacrylate, TEB 3K, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, Rocryl 400;
Described promotor is monobutyl dihydroxyl phosphorous acid vanadium or organo-metallic sulfide promotor or the mixture of the two;
Described solidifying agent is the mixture of a kind of peroxide firming agent or multiple peroxide firming agent.
Described organo-metallic sulfide promotor selected from mercapto 2-ethyl hexyl ethanoate, the different copper ester of Thiovanic acid, the different potassium ester of Thiovanic acid.
Described solidifying agent is one or more the mixture in Lucidol, the peroxo-toxilic acid tert-butyl ester, isopropyl benzene hydroperoxide, the tertbutyl peroxide.
Described oxidation inhibitor is 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, four phenmethyls (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters one of them or multiple mixture;
Described UV light absorber is 2-(2 ˊ-hydroxyl-5 ˊ-aminomethyl phenyl) benzotriazole, salicylic acid phenyl ester, 2,4 dihydroxyl benzophenone one of them or wherein multiple mixture;
Described photostabilizer is two (2,2,6, the agent of 6-tetramethyl-benzene piperidines) sebates and/or three (1,2,2,6,6-Pempiten base) phosphorous acid esters.
Described long glass fibres filament diameter is preferably 8-16 μ m, and length is 45-55mm.
The invention provides a kind of preparation technology who strengthens the vinyl resin matrix material simultaneously, its step comprises:
Step 1: vinyl resin and promotor are put into stirrer stir, it is subsequent use to treat to dissolve fully the back;
Step 2: the mixture and the solidifying agent of during production step 1 being worked good mix, and the carrying platform feed on production line is uniformly coated on by on the PET continuous film (3) that draws before continuous under tractor (11) traction through scraper (4) more continuously;
Step 3: from production line, add long glass fibres equably, and infiltration, compacting, exhaust bubble through soaking into section, long glass fibres and mixed with resin is even;
Step 4: covering film (6) on one deck PET on said long glass fibres and the resin compound, through rod (7) is controlled at the thickness that needs with resin and long glass fibres mixture;
Step 5: enter into the moulding control region of heating, wherein first moulding heating region (8) temperature is 40-90 ℃, and second moulding heating region (9) temperature is 20-50 ℃, and the 3rd moulding heating region (10) temperature is 80-150 ℃;
Step 6: cutting finished product.
Step 1 stirs for vinyl resin and promotor, auxiliary agent are put into stirrer when containing auxiliary agent in the matrix material, treats to dissolve fully afterwards subsequent use.
In order to obtain high performance material, according to the thinking of energy-conserving and environment-protective Sustainable development, the present invention combines the continuous composite sheet of long glass fibres enhancing propenoate that the advantage of thermoset, thermoplastic material is developed design.Thereby the enhancing vinyl resin composite material combination property that obtains is excellent, has that heat-drawn wire height, good weatherability, transparence are high, anticorrosive, do not produce smog during burning, can make 3 meters any continuitys with insied width and equal characteristics such as (ripple) plate.Vinyl resin has all obtained increasing substantially in material each item mechanical property that the adding long glass fibres obtains later on.
The present invention is a main raw material with vinyl resin and spun glass, is auxiliary material with promotor, solidifying agent, is main auxiliary agent with inhibitor, UV light absorber, photostabilizer mixture.Prescription has rationally improved the binding property of spun glass and resin, has improved mechanical performance of products, and the reasonable adding of various stablizers has protected the performance of material not to be damaged for a long time, has reduced product price, makes the application of material more extensive.
Technically, there are various influence factors in sheet material processing always continuously, cause quality problems easily, even processing and manufacturing can not be carried out.The present invention uses rational processing mode and flow process, makes whole production line be able to trouble-free operation.
Because vinyl resin will carry out heat treated to it being become solid process mid-early stage by liquid, thereby makes its requirement that can solidify the moulding that reaches serialization fast, but when resin reaches certain degree of cure; Must control its temperature variation; Its solidification rate will can not get control in case temperature runaways, and may cause product appearance not reach requirement, and will be smooth inadequately smooth; Even distortion on the whole, also have corresponding reduction on the performance.For the composite sheet that can in reality, use; To outward appearance still is that performance all has strict relatively specification of quality; And the present invention through a large amount of practice summary obtain preparation technology, solved this problem well, produce smooth, the smooth smooth good quality of product.
Description of drawings
For let above-mentioned purpose of the present invention, feature and advantage can be more obviously understandable, elaborate below in conjunction with the accompanying drawing specific embodiments of the invention, wherein:
Fig. 1 is preparation technology's schema of enhancing vinyl resin matrix material of the present invention.
Fig. 2 is the production line synoptic diagram.
Among the figure:
1, mixed with resin storage tank 2, mixing agitator 3, PET continuous film (following film)
4, scraper 5, long glass fibres 6, last film
7, to rod 8, the first moulding heating region 9, the second moulding heating region
10, the 3rd moulding heating region 11, tractor.
Embodiment
Enhancing vinyl resin matrix material of the present invention, the weight part of its component is: by vinyl resin 50-80 part, long glass fibres 10-45 part, promotor 0.01-4 part, solidifying agent 0.5-8 part, auxiliary agent 0-10 part;
Wherein auxiliary agent comprises one or more in inhibitor, UV light absorber, the photostabilizer.
Below be the formula table of each embodiment:
Long glass fibres is an alkali free glass fibre in the foregoing description, and filament diameter is 8-16 μ m, and length is about 45-55mm.Certainly owing to the difference of performance requriementss such as some specific intensities, the diameter of said long glass fibres and length also can be made accommodation.
Vinyl resin be for can being one or more the mixture in polymethylmethacrylate, TEB 3K, the methyl acrylate in the foregoing description, and described vinyl resin also can be acrylic acid one or more mixture such as polymethylmethacrylate, TEB 3K, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, Rocryl 400.Certainly, because different other conventional vinyl resins of also can selecting for use of material and performance.
Described promotor is one of monobutyl dihydroxyl phosphorous acid vanadium or isooctyl mercaptoacetate, the different copper ester of Thiovanic acid, the different potassium ester of Thiovanic acid, or the mixture of one of monobutyl dihydroxyl phosphorous acid vanadium and above-mentioned three organo-metallic sulfide.Certainly promotor also can be selected other conventional organo-metallic sulfide promotor for use.
Described solidifying agent also can be one or more the mixture in peroxide firming agents such as Lucidol, the peroxo-toxilic acid tert-butyl ester, isopropyl benzene hydroperoxide, tertbutyl peroxide and the azo compound.
Described oxidation inhibitor also can be 3, the mixture of 5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, four phenmethyls (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters wherein any two kinds or three kinds.
Described UV light absorber also can be the mixture of wherein any two kinds or three kinds of 2-(2 ˊ-hydroxyl-5 ˊ-aminomethyl phenyl) benzotriazole, salicylic acid phenyl ester, 2,4 dihydroxyl benzophenone;
Described photostabilizer also can be the mixture of two (2,2,6, the agent of 6-tetramethyl-benzene piperidines) sebates and three (1,2,2,6,6-Pempiten base) phosphorous acid ester.
Above-mentioned inhibitor, UV light absorber, photostabilizer are not the necessary component of material as the auxiliary agent of matrix material of the present invention, can add from the needs combination of the bells and whistles of material: promptly only add wherein one or both.
Below be the preparation technology of each embodiment, production line is as shown in Figure 2, and preparation technology's schema is as shown in Figure 1:
Embodiment one: according to the set of dispense ratio of embodiment one in the top form, vinyl resin and oxidation inhibitor, UV light absorber, photostabilizer, promotor were put into stirrer 20 minutes, treat that various auxiliary agents are subsequent use after dissolving fully.During production mixture of working good and solidifying agent are mixed; Successive is to carrying this platform feed; Be uniformly coated on by on PET (PET the is a polyethylene terephthalate) continuous film (following film) 3 that draws before continuous under tractor 11 tractions through scraper 4 again; And from production line, add long glass fibres equably, and infiltration, compacting, exhaust bubble through soaking into section, long glass fibres and mixed with resin is even; And then covering film 6 on one deck PET on the mixture, through rod 7 is controlled at the thickness that needs with resin and long glass fibres mixture.Then, enter into the moulding control region of heating, wherein the first moulding heating region, 8 temperature are 40 ℃, and the second moulding heating region, 9 temperature are 50 ℃, and the 3rd moulding heating region 10 temperature are 80 ℃; Cut finished product then, moulding is placed and measurement performance.
Embodiment two: according to the set of dispense ratio of embodiment two in the top form, vinyl resin and promotor were put into stirrer 10 minutes, treat that various auxiliary agents are subsequent use after dissolving fully.During production mixture of working good and solidifying agent are mixed; Successive is to carrying this platform feed; Be uniformly coated on by on the PET continuous film 3 that draws before continuous under tractor 11 tractions through scraper 4 again; And from production line, add long glass fibres uniformly, and infiltration, compacting, exhaust bubble through soaking into section, long glass fibres and mixed with resin is even; And then covering film 6 on one deck PET on the mixture, through rod 7 is controlled at the thickness that needs with resin and long glass fibres mixture.Then, enter into the moulding control region of heating, wherein the first moulding heating region, 8 temperature are 50 ℃, and the second moulding heating region, 9 temperature are 20 ℃, and the 3rd moulding heating region 10 temperature are 150 ℃.Cut finished product then, moulding is placed and measurement performance.
Embodiment three: according to the set of dispense ratio of embodiment three in the top form, vinyl resin and oxidation inhibitor, UV light absorber, photostabilizer, promotor were put into stirrer 15 minutes, treat that various auxiliary agents are subsequent use after dissolving fully.During production mixture of working good and solidifying agent are mixed; Successive is uniformly coated on by on the PET continuous film 3 that draws before continuous under tractor 11 tractions through scraper 4, and from production line, adds long glass fibres uniformly to carrying this platform feed; Through compacting, the exhaust bubble that soaks into section; Long glass fibres and mixed with resin is even, and then on mixture, cover one deck PET film 6, through rod 7 is controlled at the thickness that needs with resin and long glass fibres mixture.Enter into the moulding control region of heating then, wherein the first moulding heating region, 8 temperature are 90 ℃, and the second moulding heating region, 9 temperature are 50 ℃, and the 3rd moulding heating region 10 temperature are 80 ℃.Cut finished product then, moulding is placed and measurement performance.
Embodiment four, according to the set of dispense ratio of embodiment four in the top form, vinyl resin and oxidation inhibitor, UV light absorber, photostabilizer, promotor put into stirrer 15 minutes, treat that various auxiliary agents are subsequent use after dissolving fully.During production mixture of working good and solidifying agent are mixed; Successive is uniformly coated on by on the PET continuous film 3 that draws before continuous under tractor 11 tractions through scraper 4, and from production line, adds long glass fibres uniformly to carrying this platform feed; Through compacting, the exhaust bubble that soaks into section; Long glass fibres and mixed with resin is even, and then on mixture, cover one deck PET film 6, through rod 7 is controlled at the thickness that needs with resin and long glass fibres mixture.Enter into the moulding control region of heating then, wherein the first moulding heating region, 8 temperature are 45 ℃, and the second moulding heating region, 9 temperature are 40 ℃, and the 3rd moulding heating region 10 temperature are 100 ℃.Cut finished product then, moulding is placed and measurement performance.
We have also done Comparative Examples one simultaneously: the resin among the embodiment one is not added spun glass, and according to same Production Flow Chart, preparation and measurement performance.
Comparative Examples two: third resin among the embodiment two is not added spun glass, according to same Production Flow Chart, preparation and measurement performance
Comparative Examples three: the resin among the embodiment three is not added spun glass, according to same Production Flow Chart, preparation and measurement performance
Comparative Examples four: the resin among the embodiment four is not added spun glass, according to same Production Flow Chart, preparation and measurement performance
And as follows with correlated performance test tabulation:
This shows that the long glass fibres that obtains according to proportioning of the present invention and preparation technology strengthens the vinyl resin matrix material and has excellent more mechanical property and over-all properties.Its preparation technology can prepare the continuous sheet material that long glass fibres strengthens the vinyl resin matrix material rationally, smoothly effectively simultaneously.
Claims (9)
1. one kind strengthens the vinyl resin matrix material, it is characterized in that the weight part of its component is: by vinyl resin 50-80 part, long glass fibres 10-45 part, promotor 0.01-4 part, solidifying agent 0.5-8 part, auxiliary agent 0-10 part;
Wherein auxiliary agent comprises one or more in inhibitor, UV light absorber, the photostabilizer;
Described long glass fibres is an alkali free glass fibre.
2. enhancing vinyl resin matrix material according to claim 1 is characterized in that:
Described vinyl resin is one or more a mixture of polymethylmethacrylate, TEB 3K, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, Rocryl 400;
Described promotor is monobutyl dihydroxyl phosphorous acid vanadium or organo-metallic sulfide promotor or the mixture of the two;
Described solidifying agent is the mixture of a kind of peroxide firming agent or multiple peroxide firming agent.
3. enhancing vinyl resin matrix material according to claim 2 is characterized in that: described organo-metallic sulfide promotor selected from mercapto 2-ethyl hexyl ethanoate, the different copper ester of Thiovanic acid, the different potassium ester of Thiovanic acid.
4. enhancing vinyl resin matrix material according to claim 2 is characterized in that: described solidifying agent is one or more the mixture in Lucidol, the peroxo-toxilic acid tert-butyl ester, isopropyl benzene hydroperoxide, the tertbutyl peroxide.
5. according to each described enhancing vinyl resin matrix material in the claim 1 to 4, it is characterized in that in the described auxiliary agent:
Described oxidation inhibitor is 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, four phenmethyls (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters one of them or multiple mixture;
Described UV light absorber is 2-(2 ˊ-hydroxyl-5 ˊ-aminomethyl phenyl) benzotriazole, salicylic acid phenyl ester, 2,4 dihydroxyl benzophenone one of them or wherein multiple mixture;
Described photostabilizer is two (2,2,6, the agent of 6-tetramethyl-benzene piperidines) sebates and/or three (1,2,2,6,6-Pempiten base) phosphorous acid esters.
6. according to each described enhancing vinyl resin matrix material in the claim 1 to 4, it is characterized in that: described long glass fibres filament diameter is 8-16 μ m, and length is 45-55mm.
7. according to each described enhancing vinyl resin matrix material in the claim 5, it is characterized in that: described long glass fibres filament diameter is 8-16 μ m, and length is 45-55mm.
8. preparation technology who strengthens the vinyl resin matrix material is characterized in that step comprises:
Step 1: vinyl resin and promotor are put into stirrer stir, it is subsequent use to treat to dissolve fully the back;
Step 2: the mixture and the solidifying agent of during production step 1 being worked good mix, and the carrying platform feed on production line is uniformly coated on by on the PET continuous film (3) that draws before continuous under tractor (11) traction through scraper (4) more continuously;
Step 3: from production line, add long glass fibres equably, and infiltration, compacting, exhaust bubble through soaking into section, long glass fibres and mixed with resin is even;
Step 4: covering film (6) on one deck PET on said long glass fibres and the resin compound, through rod (7) is controlled at the thickness that needs with resin and long glass fibres mixture;
Step 5: enter into the moulding control region of heating, wherein first moulding heating region (8) temperature is 40-90 ℃, and second moulding heating region (9) temperature is 20-50 ℃, and the 3rd moulding heating region (10) temperature is 80-150 ℃;
Step 6: cutting finished product.
9. the preparation technology of enhancing vinyl resin matrix material according to claim 8 is characterized in that: step 1 stirs for vinyl resin and promotor, auxiliary agent are put into stirrer, treats to dissolve fully afterwards subsequent use.
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| CN2012100103583A CN102558728A (en) | 2012-01-13 | 2012-01-13 | Reinforced acrylic resin compound material |
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| CN2012100103583A CN102558728A (en) | 2012-01-13 | 2012-01-13 | Reinforced acrylic resin compound material |
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| WO2014089973A1 (en) * | 2012-12-13 | 2014-06-19 | 苏州多凯复合材料有限公司 | Frp board and manufacturing method thereof |
| CN104985838A (en) * | 2015-05-27 | 2015-10-21 | 江苏盖世智能采光科技有限公司 | Plate production device and method |
| CN105140327A (en) * | 2015-06-30 | 2015-12-09 | 杭州福斯特光伏材料股份有限公司 | Heat radiation backboard for photovoltaic assembly |
| FR3030547A1 (en) * | 2014-12-22 | 2016-06-24 | Arkema France | LIQUID (METH) ACRYLIC SYRUP, PROCESS FOR THE IMPREGNATION OF A FIBROUS SUBSTRATE BY THE SAME, AND COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF THE IMPREGNATION SYRUP |
| CN105778377A (en) * | 2016-05-11 | 2016-07-20 | 南京京锦元科技实业有限公司 | Glass fiber reinforced polyacrylic resin composite material |
| CN107283880A (en) * | 2017-08-11 | 2017-10-24 | 振石集团华美新材料有限公司 | A kind of production equipment of glass fiber reinforced plastic flat plate door skin and preparation method thereof |
| CN107903553A (en) * | 2017-12-04 | 2018-04-13 | 青岛岩康塑料机械有限公司 | Preparation method with toughness, the acrylic resin of hardness under a kind of low temperature |
| CN113004645A (en) * | 2021-02-24 | 2021-06-22 | 东莞智昊光电科技有限公司 | Thermosetting material for LED support, LED support and preparation method thereof |
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| WO2014089973A1 (en) * | 2012-12-13 | 2014-06-19 | 苏州多凯复合材料有限公司 | Frp board and manufacturing method thereof |
| FR3030547A1 (en) * | 2014-12-22 | 2016-06-24 | Arkema France | LIQUID (METH) ACRYLIC SYRUP, PROCESS FOR THE IMPREGNATION OF A FIBROUS SUBSTRATE BY THE SAME, AND COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF THE IMPREGNATION SYRUP |
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| CN107283880A (en) * | 2017-08-11 | 2017-10-24 | 振石集团华美新材料有限公司 | A kind of production equipment of glass fiber reinforced plastic flat plate door skin and preparation method thereof |
| CN107903553A (en) * | 2017-12-04 | 2018-04-13 | 青岛岩康塑料机械有限公司 | Preparation method with toughness, the acrylic resin of hardness under a kind of low temperature |
| CN113004645A (en) * | 2021-02-24 | 2021-06-22 | 东莞智昊光电科技有限公司 | Thermosetting material for LED support, LED support and preparation method thereof |
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Application publication date: 20120711 |
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